Cement composition and process of making same



Patented Aug. 9, 1949 UNITED, STATES EXAM CEMENT COIHPOSITION AND PROCESS OF MAKING SAME Donald R. MacPherson, University Heights, Ohio,

assignor to The Master Builders Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Application October 13, 1945, Serial No. 622,237 (9312 W T 10 Claims. (01. 106-90) 2 2 This invention relates to hydraulic cement compositions and to a method of making the same. It particularly relates to the method of hydra? c cement and to a method of preparm cemen compos ons having improved weatherresistant properties.

It has been known that certain materials, such for example as a certain saponifiable resin, the long-chain alkyl sulfate sucfi as lafi'ryfsbdium ahd'tli like, when added to aTEnTiitBfifi position in relatively small amounts cause the cement composition to entrain a small amp ant air, which surprisingly exerts'a'inarked improvelfifit in the ability of the concrete to withstand freezing and thawing cycles. Other materials, generally designated as grinding aids, have been proposed which exert niark d'shortening of the time required for grinding cement clinker. The alr-entraining materials heretofore proposed, as far as I am aware, either have been found to lose a substantial proportion of their efi'ectiveness when ground with cement clinker or have had no noticeable function as grinding aids, in fact they varies, with the result that the amount 'of entrained air in the concrete becomes variable and it is very diflicult, if not impossible, to control within narrow limits. It is an object of the present invention to prode an air-entrainin a ent or a class of air-entraining agents wffich may be ground with cement without losing their effectiveness.

It is another object of the present invention to provide air-entraining agents which may be ground with the cement without losing their effectiveness and which have no deleterious efiect on the rate of grinding or on any additional grinding aids which may be present.

It is a further object of the present invention to provide a grinding aid which facilitates the 5 be incorporated grinding of cemen 0 er to provide a greater amount of cement of a given fineness in a given time or to provide a cement of greater fineness in a given time, which grinding aid also gives to the o sisting of Ion -chain ali hatic dicarbo which contain besides the two carbogyl oups on a hy ocar on on sa ts and esters thereof, and 31 till i 35 monovalent metal radical or an orgamc air that is formed in the mix varies with the mix design, 1. e., the ratio of sand to total aggregate. As the sand to total aggregate ratio increases, the amount of air entrained and retained at a 5 given consistency is usually increased. Therefore,

to provide a desirable amount of air in the concrete, one had heretofore to specify the mix design, the type of aggregate, etc.

It is a further object 01' the present invention to provide an air-entraining agent which may be to total aggregate ratios.

The above and other objects, which will be apparent from the following description of the invention, are accomplished by incorporating in the went one or more members of the group conlic acids s ation res dues obtained from the re arati on of dlafi fiatic or dialkyl esters of such long-chain acids. Hie general formula of the ac1dfsj'sal I and esters is c 0 0x k R/ \COOY where R. is a mggocarbon group, preferably an aliphatic hydrocarbon group, and X and Y are hydrogen a metal, the equivalent of a on pre erably an a1 1 group. The hydrocarbon chain between car oxyl groups should preferably have a length of at least 5 or g carbon atoms, and when it is longer an 12 to 14 carbon atoms the each 40 activity of the compounds appear to be adversely aflected. When the carbon chain is saturated, the preferred compounds have a carbon chain of '7 to 10 carbons between carboxyl groups; but, w e'n' ecar on-to-carbonchain containsanole fln group, a chain of 9 to 12 carbons is preferred.

t e long-c a dicar oxy c acids and derivatives, sebacic acid and its derivatives appeartobe outs an ng. Sebacic acid and/or its soluble I 1 or potassium sebacate, may

salt, such as so u bh the cement cl er erc -e grinding thereof 0" corporated aftg; 33m mixample in e preparation 0 cement, concrete or mortar mixes. Theesters oi sebacic acid, and pecialy the s illr sidu fi i isii t p concrete or mortar made therewith air-entraining sebacic acid esters as obtained in the manufacture propertiea of an order of magnitude sufficient to improve substantially its ability to withstand freezing and thawing.

Another disadvantage of most air-entraining bf's'ebacic'acid esters by reaction of sebacic acid and an alcohol, on the other hand surprisingly have little air-entraining properties when incorporated with the ground cement in the preparaagents that I am aware of is that the amount of tion of concrete or mortar mixes; but, when they are ound with the clinker in preparing the cemen%, they are found to Be highly desirable.

Of all the aforementioned sebacic compounds, the distill tion residue obtaine from stills util- 4 grinding efllciency. However, for some commercial applications, .05% gives about the maximum amount of air desired in cement, mortar or concrete mixes. Further increases in grinding ized in 'e prepara ion an purifica l. "of 1 ut l eificiency may be obtained by also incorporating EeBad ale 1S found to be most desirable 'i'orlncor an Mng aig with the clinker. Such poration with the cement clinker. This material grinding aids are preferably hydroxy 033221151- usually contains a substantial proportion, somemg fii liphwms sucH as times as much as 75% to 85%, MW 1 col e ers, gmwmwamediol and e (based on the recovery of butyl a co 0 an e 1 e, su s itu ic acids an erivatives saponification value of the materials). It exerts thereo suci1*a'?iiicy1i"ac1 salicylafis, etc., a most desirable effect when incorporated with which are usually'flsea ffiaimounfibefieen .0l% the cement clinker and ground; it has relatively and .1% by weight of the cement. no appreciable effect when added as an additive Example 2 to cement or mortar mixes.

This still residue, like other of the aforemen- A given cement clinker was divided into two (med dibasic aliphatjq acid or sebacic batches and ground for the same length of time poundsf-ffimdigg" 5 c m the Sodium salt as in Example 1, one batch serving as the control thereof, etc Show g' E'Hi-EH wggmi' and the other batch having added thereto .05% amounts not substantially exceeding .1% of the by Welght of the cement of fihafii 3.251? The weight of the cement and preferably Should be specific surface of the cement obtained from the present in amounts of about .02% to about .05% Plain grind was 1600 whereas the Specific or 06% by weight of the cement As little as surface of the cement obtained from the clinker -01% of the sebacic acid compound or still resi containing .05% of sebacic acid was 11740 cmF/K, due from the preparation above exerts an apprerepresentmc, an increase in speclfic surface ciable improvement on cements, but in amounts over the mam grmdless than .005% has little effect. Example 3 Di asic aliphatic acid compounds other than sebacic acid and its alkali metal salts, such as To illustrate h 9 ium ammonium or otassium sebacates which still lfikillii lfw l fii fi fibw a w en ground izs zisa iiszzzi include th a esters, such a d l, r dibutyl, dihfi esters of sebacic f l (5% ground Wm? 2 2 and by weight of the mar mfi' m cement of still residue were made up into conm-mm crates of two rad1cally diiferently mixeddesigns. duction of such esters are preferred. 2 x :h; g 3 i f ratio g 0 1 esan o a aggrega era 0 gfi g examples illustrate the present was 36% .to 39%. The consistency of the two mix Example 1 designs was substantially the same, although the m slump was somewhat difi'erent due to aggregate The-same Portland cement clinker was divided size. The still residue was incorporated with the into equal lots and each of the lots was separately cement clinker prior to the grinding thereof. ground for 120 minutes. One lot was ground All cements were prepared from the same clinker. without an addition and the other lots were The essential data concerning the mixtures is ground with additions of still residug gbtained shown in the following table.

srm Residue, Water- 2225 222 TotalAir, 8mm

tress g its? Mix #1 813% Z133 8 ii 1 as: 2-23 a a Man 010a 0100 39 a4 a 0. 05 a. 10 as 8.4 s

irom the gis tillation of gibgtyl eba cate in the It will be seen from the above tabulation that preparation or purification thereof. The spethe percentage of total air remains about the cific surface of the cements and the percentage same, even though Mixes #1 and #2 were radincrease in specific surface due to the grinding ically different. It will also be seen that the maxaids are also set forth in the following table: 60 imum air entrained is that obtained with 0.03% still residue. The fact that no increase in air Specific eic n content of the resultant concrete is had when Per Cent Grinding Aid Surface g gig the amount of still residue is increased to 0.05% (by wt-mmmt) "8 145; Surface 7 is of importance where a greater amount of still P151 residue is desirable as a grinding aid to gain on- Nonkmam timum efllciency without having the resultant ce- 0.01 Still Kasai:::::::::::::::::::: ifi ""63 ment entrain excessive amwnts 0f 0.03 sum Residue 1,100 3.1 0.05 can Residue 1, 810 10.4 Example 4 To illustrate the influence of sebacic acid com- It will be noted from the above tabulation that p un upon he mpr ive r h of conthe dibutyl sebacate still residue becomes procrete, two batches of mortar were prepared in gressively more efilcient as a grinding aid as the accordance with A. S. T. M. Mortar Specification quantity increases. Larger quantities of still resi- 0- e batch wa Pr p w a em n due than those shown give a further increase in of substantially the same specific surface, but it EXAMI was ground without a sebacic acid additive. The second batch was identical except for .05% sebacic acid interground with the cement. Twomdird mortar cubes were prepared from each ofthe batches. The cubes of both batches were tested for compressive strength at ages of 1 day, 3 days, 7 days and 28 days. The average values of the compressive strength of the cubes, together with other pertinent data, are shown in the following table:

The cement compositions of the present invention may also contain an acceleraiygI to in-- crease the hardening and set prope es of y active or cement-dispersing constituents of waste Compressive Strengths,

ba/sq. in. Specific Water- Addition Adam Surface Cement Airpercent bywt'cement cmd/g. by wt. byvolume None 1, 750 0.53 890 2,350 3,310 5,70) .05 Sebadc Add--- 1,740 0.53 2.0 970 2&5 3,640 5,815

Example 5 suliite li uor, or the dried residue thereof. Other cemen rsing Egenfi'f such as the whole To illustrate the eflectiveness of .01%, .03%

was m liquor. the condensatio afia} and 05% of still r siduesnwhichea an zlieiqe ds l'ia. a ene su om ac 3w formalde from the dist ation of clib itylsebacate, several batches of concrete were made utilizing cements prepared from the same clinker. The cements for the separate batches diflered only in the amount of still residue added during grinding, but the cement of Batch #1 was ground without an addition and served as a control. Cements of Batches #2, #3 and #4 were ground with .01%, .03% and .05%, respectively, of still residue. The aggregate in each case was three-quarter inch stone. slump of a twelve-inch cone, total volume of air entrained, unit weight in pounds per cubic foot of concrete, together with average compressive strengths of 6" x 12" cylinders prepared from each batch of the concrete are shown in the following table:

The cement factor, water-cement ratio,

' resul 'rrampnepr mo 1: cement dispersing agents, it is generally desirable that they bepresent in a total amount of .0596 to 5% or .6% by weight of the cement.

The preferred amount of dispersing agent is usually about .1% to 3%, although as much as .5% or .6% of some dispersing agents may be used.

The dibasic acid or sebasic acid compounds of the present invention may be mixed with dispersing agents and/or accelerator in proportion to form when added to cement 005% to .1% of the sebacic acid compound and also .05% to .5% by weight of the amount of dispersing agent and/or 1% to 2.5% or 3% by weight of the cement of an accelerator, such as calcium chloride, which accelerates the hardening and setting of the Specific ti 'ah I! Batch gg] gum gement 83$? Slump, Unit x lbs/sq. in. GaL/Sack Inches Percent 7 days 28 day! None 1, 700 4. 7s 7. 7o s 140. a o. 3 2, 520 a, 120 001 1,655 4.87 e 14:10 4.6 2,520 3,180 0.03 1,700 us em 3 140.0 8.4 2,010 3,220 0.05 1,810 5.13 am 3 141.5 8.6 2,000 3,200

l Sacks per cubic yard. {Pounds per cubic foot.

It will be seen from the above table that even though the concrete of Batches #3 and #4 contain over 8% air, the 28-day strengths are still as good as or better than the control.

The Portland cement in the above examples may be substituted by a um gg' 3s cement or other Qdraulic cement if desired.

I is seen from the above tests that the dibasic acid compounds of the present invention, particularly still residue obtained from the preparation of sebacic acid esters, have a multifold function in concrete or mortar mixes when they are incorporated with the cement during the grinding of the clinker. Thus, it is seen that the additions reduce the grinding time and energy required to prepare a cement of a given fineness. They act to improve the strength or setting properties of the concrete while simultaneously entraining air in amounts to be most desirable for increasing the resistance to freezing and thawing of concrete or mortar.

cement. Such a mixture is a particularly desirable indurating composition which may be incorporated with the cement mix at any time. When the aliphatic dibasic acid compound is a sebacic acid ester such as an alkyl ester or a still residue from the preparation of an alhl ester of sebacic acid, such as a still residue from the distillation of dibutyl sebacate, the indurating composition is preferably ground with the cement to obtain full advantages from the composition, as aforementioned.

Another desirable induratinmmposgign for addition to cement may comprise one or mofe of the aforementioned aliphatic dibasic acid compounds, such as the still residue from the manufacture or dibutyl sebacate, and a member of the' group consisting of substituted benzoic acids, salt and esters thereof W15 for example, sEH- cyiic acid, etc. as set forth in the Scripture Patents Nos. 2,360,517 and 2,264,336, with the ingredi ents proportioned to give when admixed with "7 cement D0596 to .05% or 0.1% by weight of the cement of the aliphatic dibasic acid compound and .005% or .01% to .5% of said group member or members.

While sebacic acid compounds are preferred in the exercised the present invention, other gi canboxylic acids or acid compounds having two carbci nagrsuis'jsewswutt a saturated v r' n fimqfcne may be used watch some of the be fits BI the present invention. Thus 1,10-decane dicarboxylic acid, its salts, esters mm mthe preparation of suc lasers, mayal'sbbe utilised-by substitutionTdf-aii equivalent amount of the sebacic acid compound aforementioned. The expression alkanedicagboxylig compound immerse -cerkqfi sieimereie As used herein, the term sebacic acid compound is used to designate sebacic acid, rims, ins and the still residues remaining after distillation of sebacic acid esters.

- Furthermore, it is to be understood that the particular form of product shown and described and the particular procedure set forth are prerented for purposes oi explanation and. illustration and that various modifications of said product and procedure can be made without departing from my invention as defined in the appended What I claim is:

1. In a method of making an hydraulic ceinent composition, the step which comprises incorporating with the cement during the grinding thereof 905% to 0.5% by weight of the cement of at least one member selected from the group consisting of sebacic acid, its salts and alkyl esters. 2. The method of claim 1 wherein said compound is dibutyi sebacate.

3. A dry cement comprising an hydraulic cement and at least one member selected from the group consisting of sebacic acid, its salts and alkyl esters, said compound being present in the amount of .005% to .5% of the weight of the cement.

4. The dry cement according to claim 8 wherein said compound is dibutyl sebacate.

5. The process or preparing improved hydraulic cement, concrete or motor mixes for structural purposes in which the hydraulic cement constitutes the main binding ingredient, which comprises mixing with the hydraulic cement an accelerator for increasing the hardening of the cement, and at least one member selected from the group consisting of sebacic acid, its salts and alkyl esters, said compound being present in the amount of .005% to .5% of the weight of the cement.

6. The process of preparing improved hydraulic cement, concrete or mortar mixes for structural purposes in which the hydraulic cement constitutes the main binding ingredient, which comprises mixing with the hydraulic cement an accelerator for increasing the hardening of the cement, and dibutyl sebacate, said dibutyl sebacate being present in amounts of .01% to .l% by weight of the cement in said concrete or mortar mixes.

7. The method of claim 5 wherein a cement dispersing agent is also present.

8. A mortar or concrete mix, comprising an hydraulic cement, aggregate, at least one member selected from the group consisting of sebacic acid, its salts and alkyl esters, in an amount of .01% to .l% by weight of the cement, and a cement dispersing agent in an amount of .05% to .6% by weight of the cement.

9. The mortar or concrete mix of claim 8 which also contains a member of the group consisting of substituted benzoic acids, salts and esters thereof, in an amount of .005% to .5% by weight of the cement.

10. The mortar or concrete mix of claim 8 which also contains calcium chloride and a member of the group consisting of substituted benzoic acids, salts and esters thereof, in an amount of .005%- to .5% by weight of the cement, and calcium chloride in the amount of 1% to 3% by weight of the cement.

DONALD R. MACPHERSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PA'I'ENIBI.

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